DE1597540A1 - Use of onium halides as silver halide complexing agents for stabilizing photographic silver halide images - Google Patents

Description

DR ING WOLFF H BARTELS ⁸ MONKS 221, .... AUE ....

UK. -JN-17. WULtC, .H-. BAKItLi, THIERSCHSTRASSE I

DR .. BRANDES, DR.-ING «'H'E'LD phone . · (Oen) 293297

Reg. No. 120

Eastman Kodak Company, 343 State Street, Rochester, New York State, United States of America

Use of onium halides as silver halide complex formers. for stabilizing photographic silver halide

pictures

In conventional light-sensitive photographic processing Silver halide elements are known to be the latent silver image produced in these elements by exposure first developed and then fixed, with the undeveloped light-sensitive silver salts removed. Is rapid development of exposed films or photographic papers desired or? required and very good copy persistence not required, the unexposed silver halide after being converted into compounds which, towards light,

000824/1587

Heat and moisture, which are relatively inert, are left behind in the copy. Such ⁿ fast processing method "is provided as a so-called." Known stabilization process ". The criterion for assessing the effectiveness of such stabilization method is the stability of the resultant photographic image to incubation with moisture and light.

The usual known stabilization methods have the Disadvantage that the complexing agents used have undesirable properties. For example, they often become opaque Complexes are formed or the complexing agents bleach it Silver picture off. Some of the known complexing agents are also activated by water and can therefore be aqueous Gelatin-silver halide emulsions cannot be incorporated without affecting the sensitometric properties of the respective Adversely affect the emulsion or the photosensitive layers produced from it. This through water Activatable complexing agents are also | for dry development processes not suitable. Furthermore, it has been shown that only a few known silver halide stabilizers are also found or complexing agents for the diffusion transfer process suitable, /

BATH ORIGINAL

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The object of the invention was to provide stabilizers or complexing agents indicate the stabilization or fixation of photographic silver halide images, which the disadvantages of hitherto known complexing agents and stabilizers do not have and are in the context of the most varied of photographic Let the development process be used to stabilize or fix the unexposed silver halide.

The invention was based on the knowledge that the task set can be achieved by using certain onium halides lets go.

The invention relates to the use of onium halides, consisting of organic sulfonium, sulfoxonium, Ammonium, phosphonium, boronium or siliconium halides as well as mixtures thereof in silver halide emulsion layers or these adjacent layers in concentrations of at least 0.5 moles of onium halide / mole of silver halide or in fixing solutions in concentrations of 0.1 to 60% by weight / liter of solution as a silver halide complexing agent for stabilizing silver halide photographic images.

Onium halides which can be used according to the invention can be represented by the following formulas: ^v

⁰⁰⁹⁸² * ^{/ 1587}

A '

■ R.

and

where mean:

Ä is a sulfur atom or a group of the formula SO; A * a nitrogen, boron or phosphorus atom j

A ^{w is} a silicon atom;

X is a halogen ion and

R ,, R ₂ , R ?, Rjj, Rc and individually in each case hydrogen atoms or optionally substituted amino, alkyl or aryl radicals, hydroxy radicals or älphatic or aromatic radicals with at least one older bond or an oxa group, or two of the radicals R ₁ , R ₂ , R ,, R | j, Rc and Rg slowly

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^ * ^ ¹ ° of A "a saturated or unsaturated heterocyclic ring pc. - ^ - - - ->

8AD ORIGINAL

_5- 15975 * 0

Preferred complexing agents of the formulas given are: tetraethylammonium bromide, 2-hydroxyethyltrimethyl ammonium bromide, tetraethylammonium chloride, ethyltrimethylammonium bromide, Tetramethylammonium bromide, tetrapropylammonium iodide, Methylamine hydrobromide, trimethylamine hydrobromide, tetraethylphosphonium bromide, n-butylgtriphenylphosphonium bromide and trimethylsulfonium bromide.

The onium halides used according to the invention are odorless and unusually stable to fluctuations in temperature, light and humidity. Connections that have no or have little tendency to fade silver images and non-tacky or tacky on the photographic elements being treated. they form Transparent silver halide complexes stable with silver halides.

They can be in the form of aqueous or non-aqueous fixing baths be used. They can also be used for stabilization those silver halide photographic elements which are stabilized by heating can be used. In this Trap the photographic elements contain the stable! -

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catalysts and complexing agents in a form that can be activated by heat. Furthermore, those used according to the invention can be used Onium halides also successful in diffusion transfer processes use. Finally, those used according to the invention as stabilizers and complexing agents can be used Onium halides are also housed in a developer belt used to process photographic elements will.

Are used according to the invention as stabilizers or complexing agents compounds used in the form of cold aqueous solutions for stabilizing or fixing exposed photographic If elements are used, their stabilizing or fixing effect occurs only slowly. Will you on the other hand, when used in the form of hot aqueous solutions, they can rapidly produce an exposed photographic element to stabilize or fix.

If the onium halides used according to the invention are in

if the form of a solution is used, e

preferably in concentrations of 5 to

40 percent by weight, based on the solution, was used. /

BATH ORIGINAL

The onium halides can be used both in the form of aqueous solutions and in the form of solutions in a non-aqueous liquid or low melting solvent "means solvents which melt at room temperature and fest.sind to 15O ⁰ C. ·

Suitable, non-aqueous, liquid solvents in which the onium halides used according to the invention already develop a favorable stabilizing effect at room temperature are, for example, formamide, N, N-dimethylformamide, dimethyl sulfoxide and tetramethylene sulfone.

Low-melting solvents, such as, for example, succinimide, sulfamide, acetamide and urea, which are solid at room temperature, are also excellent solvents for the complexing agents and stabilizers used according to the invention. They can be used together with the Stabilizer and complexing agent can be applied directly to the photographic material or placed in a special developer belt. Thus, the stabilization or fixation by simply heating the photographic Material or by contacting the photographic Material with a hot developer tape.

Other suitable non-aqueous solvents are, for example: alcohols, ketones and nitriles.

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BATH

The silicon halide complexing agents used according to the invention are preferably used in a low-melting, non-aqueous solvent and a polymeric binder, through which the melted solvent diffuses, can be applied and used as an image stabilizing layer on a photosensitive photographic Silver halide emulsion layer applied. The low-melting solvent is solid at room temperature and the complexing agents contained therein are inactive. When heated, the solvent melts and allows diffusion of the complexing agent into the photographic emulsion layer, where it is mixed with the unexposed silver halide reacts and thereby causes stabilization. . .

The joint use of succinimide and tetraethylammonium bromide or tetraethylphosphonium bromide has proven to be particularly advantageous proved, since this stabilizer or fixing mixture has an extremely low tendency to Has fading of the silver image. Succinimide forms with tetraethylammonium bromide and tetraethylphosphonium bromide a clathrate that is extremely difficult to liquefy, which prevents the silver image from fading. Images stabilized with such mixtures, for example, fade more slowly than those fixed with alkali thiosulfates Pictures.

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The use of quaternary ammonium compounds in photographic processes is known per se. From US Pat. No. 3,093 # 79, for example, a method is known in which a fixed photographic image is then treated with a solution of a quaternary ammonium halide in order to prevent the image from fading and yellowing and to prevent the image from being caused by bacteria to protect caused destruction. The quaternary salt used in the known process in low concentrations (1-2 %) reacts with all of the remaining thiosulphate of the fixing stage, apparently an insoluble, immobile molecule being formed which cannot react with the sulphide ions originating from the air or with the remaining sulphide ions.

In the process of the invention, on the other hand, the quaternary ammonium compounds are used in considerably higher concentrations. In doing so, they react with the unexposed silver halide to form stable complexes of the probable formula Q AgXp ⁰ . The complex can either be left in the photographic element or removed by washing away.

From U.S. Patents 2,238,631, 2,238,632 and 2 288 586 Is the use of quaternary phosphonium iodides

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ternary sulfonium iodides and quaternary ammonium iodides for controlling the yellow fogging of photographic emulsions are known. These compounds are also used in only low concentrations in order to prevent the precipitation of a yellow precipitate in the emulsion layer as a result of the formation of colloidal silver in the developing baths.

There are two types of stabilizers known to exist with Silver halides form complexes. This includes once the silver halide complexes insoluble with silver halides and, on the other hand, those soluble with silver halides Complex forming stabilizers,

Insoluble silver halide complexes which are usually opaque and therefore generally to stabilize photographic Images that are unsuitable are caused by the reaction of thioglycolic acid, Thiosalicylic acid and other mercapto compounds obtained with silver halides

Alkali thiosulfates, alkali thiocyanates, thiourea and In contrast, certain thiourea derivatives convert silver halides into soluble complexes

The stabilizers used in the present invention can be used both as photographic silver halide emulsion films are also incorporated into these neighboring layers

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ORIGlNAL BATHROOM

the stabilizers housed in the emulsion layer the emulsion layer can be prepared by customary application of an aqueous emulsion containing the stabilizers to a support at or below room temperature can be generated without the emulsion being pre-stabilized. In contrast, the stabilizers in one of the layer separated from the emulsion layer, solutions of the stabilizers in solid, low-melting, non-aqueous solvents are used.

Solutions of the stabilizers can also be a so-called Developer baYid are incorporated. The stabilization of the photographic element occurs in such a case in that the developer tape soaked with the stabilizer solution with the exposed photographic element in Contact is brought. On the other hand, however, can also be a dry developer tape can be used, which contains the stabilizer and a low-melting solvent, for example succinimide, sulfamide, urea or acetamide, contains. After contacting the photographic element and heating, the stabilizer is activated.

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BATH

The photographic element or developer belt containing the stabilizer can also optionally contain a Developers are incorporated. Such silver halide developers which are usually silver halide reducing Compounds are, for example: 3-pyrazolidones, such as l-phenyl-3-pyrazolidone and l-phenyl - ^. 'L-dimethylpyrazolidone; Salts of ascorbic acid such as sodium isoascorbate; p-phenylenediamine hydroquinones; N-methyl-p-aminophenol sulfate; Pyrocatechol and the like. Particularly advantageous Developer compounds are l-phenyl-3-pyrazolidone and sodium isoascorbate · In the presence of the developer in one the photographic element or developer belt containing stabilizers or complexing agents used according to the invention can thus be used simultaneously in a single step both a development and a stabilization of the silver halide can be carried out

The silver halide complexing agents used in the present invention can also be used advantageously in diffusion transfer processes. In this process, a photographic material is first exposed and then developed. The unexposed silver halide is then bound or stabilized as a complex in the non-image areas of the photographic material and then transferred to an active seed-containing one

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Receiving sheet transferred by diffusion. Upon contact with the active nuclei, the silver halide complexes dissociate, whereby silver ions are set free, which are Let develop into a silver image on the receiving sheet.

The complexing agents and stabilizers suitable for this purpose must be able to transfer the entire unexposed Silver halide allow and, more importantly, the complex obtained in the stabilization must be upon contact can dissociate with the active germs of the receiving sheet. Most silver halide stabilizers and chelating agents form complexes with silver halides which are difficult or insufficient when they come into contact with the receiving sheet dissociate. Those with the stabilizers used according to the invention Complexes formed or complexing agents, on the other hand, dissociate upon contact with the active nuclei of the Receiving sheet light and thus enable an excellent diffusion transfer.

The complexing agents and stabilizers used according to the invention can optionally also be dissolved in mixtures, complexes or eutectics composed of various solvents. With a suitable choice of the solvent or mixtures of solvents can

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in non-aqueous development processes many variables such as temperature, maximum density, the Degree of obfuscation and the gamma values, coordinate as desired «

The photographic ones that can be stabilized with the new stabilizers Silver halide emulsions can be used in catfish customary in emulsion production, for example by Digestion with natural, active gelatine or with the addition of various sulfur and / or gold compounds · The emulsions can also be mixed with salts of noble metals of group VIII of the periodic table of elements with atomic weights greater than 100 sensitis · Those that can be stabilized by the new stabilizers Emulsions can be surface-active or predominantly internal sensitivity. The emulsions can also be Contain susceptibility-enhancing additives such as polyethylene glycols or thioether sensitizers.

Further additives may according to the invention, be stabilized emulsions conventional additives such as gelatin plasticizer, curing agent, and BescHchtungshilfsmittel containing ^i. The emulsions can be X-ray emulsions as well as other, non-optically sensitized emulsions

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as well as orthochromatic, panchromatic or IR-sensitive emulsions. The individual additions can Emulsions are added before or after the addition of sensitizing dyes, if any are used.

A wide variety of customary silver halides, such as, for example, silver bromide, silver iodide, silver chloride, or mixed silver halides, such as silver chlorobromide and silver bromoiodide, can be used as light-sensitive salts to produce the emulsions. The emulsions can also be color photographic emulsions and can be used to make color photographic elements and thus contain color-forming couplers, or they can be used to make emulsion layers which are developed in solutions containing couplers or other color-forming substances. The emulsions may also be from the United States Patent * Mlschpakettyp described 2698 79 ¹ or the type described in US Patent 2,592,243 Nischkorntyp.

The binders of the emulsions can be selected from the usual known polymers exist, such as. B. from gelatin, colloidal albumin, cellulose derivatives and synthetic Hansen, such as polyvinyl compounds. Typical suitable

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-Id-

Colloids are, for example, polyvinyl alcohol, hydrolyzed Poly vinyl acetate, ♦ hydrolyzed cellulose esters, water-soluble ethanolamine cellulose acetates, polyacrylamides, Copolymers with a 3 to 6 OJS η content of combined acrylic amalgamation units, copolymers Alkyl acrylate and acrylic acid, vinyl alcohol blended polymers with urethane carboxylic acid or cyanoacetyl groups, or polymers, which in the polymerization of a protein or a saturated, acrylated protein with a vinyl group containing monomers of the type described in U.S. Patent 2,852,382. Such polymers can be used in the form of latices or hydrosols. . '

The following examples are intended to illustrate the invention in more detail.

The following three examples show the effectiveness of the stabilizers used according to the invention as fixing agents.

example 1

By dissolving 2-Hydroxyäthyltrimethylammoniumbromid in Formamide was made into a 20% solution. A photographic film coated with a gelatin-silver chloride emulsion

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Paper (with 8.29 mg of silver per dm of support surface) immersed in the solution for one minute at room temperature. The paper was then soaked in water for 5 minutes washed, whereupon the silver content was determined. The SiI

The excess content was 0.17 mg per dm of support surface, which shows that after a treatment lasting only one minute and washing for 5 minutes, practically all of the silver was removed ^{by means of the "Fid.erlösung 1" produced using the stabilizer.}

Example 2 (comparative example)

A 20 # solution was prepared by dissolving 2-HydroxyäthyltrimethylammoniumbrOmld in water. A sample of the silver chloride paper described in Example 1 was immersed in the resulting solution at room temperature for 5 minutes and then washed in water for 5 minutes. The silver content was then determined. The silver content was still 6.78 mg per dm ^{2 of support} surface. From this it can be seen that a solution of the quaternary ammonium salt in water has poor pixier properties at room temperature.

009824/1587 bathroom

Example 3 ' ^!

Examples were repeated, except that the silver chloride paper described in Example 1 was ^{immersed for one minute in a 90 °} C. solution of the quaternary ammonium salt. The silver content of the washed sample was again determined. This was still 0.27 mg per dm ^{2 of support} surface. It follows that 2-hydroxyethyltrimethylammonium bromide is a good fixing agent in hot water.

Example 4

This example describes the manufacture and use of a photographic element containing one of the stabilizers used in the present invention.

First, a solution was made from the following components:

A. Succinimide 30 g

l-phenyl-3-pyrazolidone 3g

Sodium isoascorbate 5g j

Water 40 g.

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159T540

The resulting solution was dissolved in 186 g of a 7X solution of ethyl cellulose dispersed in toluene "

Furthermore, a solution was made up of the following components:

B. Succlnimide 6 g SuIfamid 2 g Tetrapropylammonium iodine 6 g water 3 g

The solution B obtained would also be in 186 g of a 72igen solution of ethyl cellulose in toluene dispersed.

The two dispersions A and B were in equal parts mixed together and then using a 0.254 mm coating knife applied to paper coated with a gelatin-silver chloride emulsion. After the dispersion had dried, the photographic element obtained was exposed for 10 seconds to a Ίθ Watt bulb lamp through a line copy negative and then heated for 5 seconds on a 155 ° C. mandrel. The copy obtained was used for a week with a fluorescent table lamp exposed without it being too

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destruction of the image or darkening of the. Background came.

If the quaternary ammonium salt was omitted in "Solution B", no stabilization was achieved, i.e. H. the copy darkened very quickly when exposed to room light.

Example 5

A solution was made from the following ingredients:

Succinimide, 30g

1-phenyl-3-pyrazolidone 3 g Sodium soascorbate 5g

Tetrapropylannonium iodide 8 g Water 40 g

The solution obtained was dissolved in 186 g of a 7 * strength solution of Xthyl cellulose dispersed in toluene.

The obtained dispersion was made using a 0.203 mm coating knife applied to a paper having a gelatin-silver chloride emulsions layer.

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The obtained photographic element was left for 10 seconds by means of a 40 watt bulb lamp through a line copy negative exposed and then heated for 10 seconds on a 155 ° C hot mandrel. Here already appeared an image after a few seconds. The processed photographic element was now viewed from a distance of 15.24 cm Exposed for 24 hours with a fluorescent 20 watt table lamp » The image was neither destroyed nor increased in the degree of obfuscation.

Example 6

A solution was made from the following ingredients:

Succinimide 15 g l-phenyl-3-pyrazolidone 1.5 g

Sodium isoascorbate 2.5 g

Tetraethylammonium bromide 6.5 g

Water 15 g

The solution obtained was dissolved in 93 g of a 7% strength solution of ethyl cellulose dispersed in toluene.

098 24/158 7. BAb msomm.

The dispersion obtained was applied to paper having a gelatin-silver chloride demulsion layer using a 0.203 mm coating knife and dried. The photographic material thus obtained was carried out for 10 seconds using a 40 watt bulb lamp exposed through a bar copy negative and then heated on a 155 ° C mandrel for 3 seconds. The developed image was then taken from a distance of 15.24 cm Exposed for 24 hours using a fluorescent 20 watt table lamp. The image was not destroyed nor to an increase in the degree of concealment.

Example 7

A sample of the photographic material described in Example 6 was stored at a relative humidity of 50% and a temperature of 73 ^° C. for 6 weeks. It was then exposed to light and heated to 155 ° C for 3 seconds. The quality of the developed and stabilized image obtained was almost as good as the image obtained according to Example 6 · It follows that the paper coated in the catfish described had good storage stability · '

009-824 / 1887 '

BellPltl 8

J A solution was prepared from the following components:

Succinlmid 15.0 G Watter 20.0 G l-phenyl-3-pyraeolidone 1.5 G Sodium isoaseorbate 2.5 G 2-HydroxyftthyltriMthyl-
amoniunutohlorld 4.0 G

The resulting solution was in 93 g of a 7ίigen solution of Ethyl cellulose dispersed in toluene.

The resulting dithering was applied to paper widening gelatin-silver chloride emulsions by means of a 0.203 mm coating and dried 155 ° C hot thorn received · A gray-black Image preserved with a yellow background. The copy was stable to fluorescent light. Neither the picture nor did the image background change with exposure.

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BATH

Example 9

A dispersion, as described in Example 8, was applied by means of a 0.152 mm coating knife to paper (3.23 XS 'per dm ^{2 of support} surface) which had been vapor-deposited with silver bromide in a vacuum. Bulb lamp exposed through a bar copy negative and then heated for 3 seconds on a 155 ° C mandrel. A gray-black image on a brownish background was obtained. The copy was stable to fluorescent light. The image quality did not change, nor did the fogging increase.

Example 10

This example illustrates the use of quaternary ammonium halides as silver halide complexing agents in US Pat non-aqueous solvents in a diffusion transfer process.

A solution was prepared from the following components:

Sodium isoascorbate 1-phenyl-3-pyrazolidone

2-hydroxyethyltrimethylammonium bromide

Formamide

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3.0 G 0.5 G 5.0 G 50.0 ml

A piece of paper coated with a Qelatine silver chloride emulsion was exposed for 30 seconds in a copy box using a 40 watt lamp through a line copy negative. The solution described was then brushed onto the surface of the photographic paper using a camel hair brush. The surface of a receiving sheet was then brought into contact with the surface of the moistened paper. The JtIINMXXKX "sandwich ¹¹ thus obtained was 2 seconds on a ll» 0 ^G C hot mandrel is heated. Subsequently, the two papers separated again. On have been the Receive) latt was a brown-black positive of the existing on the exposed paper image imaged.

Example 11

A solution was made from the following ingredients ί

Succinimide 15 »0 g Sodium isoascorbate, 2.5 g

1-phenyl-3-pyrazollonone 1.5 g

Tetraethylammonium bromide 9.0 g

Water 20.0 g

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The solution obtained was in 93 g of a 7 * strength solution of Ethyl cellulose dispersed in toluene.

The resulting dispersion was coated onto a sheet of paper coated with a veiled direct positive silver chloride emulsion of the type described in U.S. Patent 2,541,472 using a 0.102 mm coating knife and dried. The photographic material obtained was then exposed for 45 seconds by means of a nitrophot lamp (No. 2), a yellow film being inserted between the lamp and the negative. The exposed photographic material was then heated for 3 seconds on a 155 ° C hot mandrel. A positive copy of the "positive ¹¹ image was obtained. The copy was stable to fluorescent light. The image was neither destroyed nor was there an increase in the background image." ite).

Example 12

A solution was made on the following ingredients:

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Succinimide 10.0 g. Methanesulfonamide 5.0 g

Cotton wool 20.0 ml

1-phenyl-3-pyratolidone 1.5 g

Sodium ltoate corbate 2.5 g Tttraftthylammonium bromide 10.0 g

The solution obtained was in 93 g of a 7Ϊ solution of Xthyleellulote dispersed in toluene.

The obtained dispersion was made using a 0.152 mm coating meter is applied to paper having a gelatin-silver chloride emulsion layer and dried up. The photographic material obtained was then for 10 seconds using a 40 watt bulb lamp

through a line copy negative and exposed for 3 seconds on "hot inea 155 ⁰ C Dorn heated · Here, a bräunet on white background image was obtained. The paper was incubated for 2Ί hours at a relative humidity of 100 ° C and a temperature of 75 ° C without the image cracking and the background density increasing «

Example 13

A solution was made up of the following ingredients:

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BATH ORIGINAL

Succinimide 6.0 G SuIfamid 2.0 G water 3.0 G Tetrapropylamraonium iodide 8.0 G

The resulting solution was dissolved in 35 g of a 14 lgen solution of Ethyl cellulose dispersed in toluene.

The resulting dispersion was coated onto photographic paper containing a layer of AgCl, gelatin, succinimide 1-phenyl-4-methyl-3-pyrazolidone and sodium isoascorbate using a 0.102 mm coating knife. The photographic paper obtained was then exposed for 30 seconds through a line copy negative by means of a 40 watt bulb lamp and ^{heated for 4 seconds on a 155 °} C. mandrel. A black image on a yellow background was obtained. The paper was exposed to fluorescent light for 24 hours without destroying the image and increasing the background density.

In a comparative experiment, the described photographic paper was not compared to that described above produced dispersion coated. One received after

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Exposure and heating an excellent image, the image background however, darkened greatly when exposed to visible light.

Example 14

First, a silver halide emulsion was made as follows manufactured?

(a) 1 * 1 g of a silver chloride coagulum containing 15 g of gelatin and 1 mol of silver per 370 g of emulsion in 100 g verichrome gelatin, which additionally contains 7 g succinimide contained, dispersed.

(b) A solution was prepared from the following ingredients:

Succinimide 15 »0 g

Water 20.0 g *

1-phenyl-3-pyrazolidone 1.5 g

Sodium isoascorbate. 2.5 g

Tetrapropylammoniura iodide. 8.0 g

10 parts (a) were mixed with 5 parts (b) and immediately then on one with a gelatin interlayer

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BAD ORiGIHAL

(subbed layer) provided polyethylene terephthalate film carrier applied. After the layer was dried, the resulting photographic material became a for 5 seconds Distance of 3 * 48 cm with a NItrophot lamp (No. * 2) and exposed for 10 seconds on a 155 ° C hot mandrel heated · A developed and stabilized image was obtained.

Example 15

A solution was made from the following ingredients:

Succinimide 15.0 g Sodium isoascorbate 2.5 g

l-phenyl-3-pyrazolidone _f * ~ 1.5 g n-butyltriphenylphosphonium

broald 10.0 g

Water 20.0 g

The resulting solution was in 93 g of a Tilgen solution of Ethyl cellulose dispersed in toluene.

The resulting dispersion was measured for a Qelatjjie silver using a 0.203 mm caliper knife.

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chlorldemu leionsschicht exhibiting paper applied. To After the dispersion had dried, the photographic material obtained was exposed through a line image original and then heated to 155 ° C for 5 seconds. Hereby a developed and stabilized image was obtained

Example 16

A solution was made from the following Beatand parts »

Suociniaiid 15 »0 g Sodium isoascorbate 2.5 g.

1-phenyl-3-pyrazolidone 1.5 g

Tetraethylphoephinium bromide 9.0 g

Water 20.0 ml

The resulting solution was dissolved in 93 g of a 7Jfigen solution of Ethyl cellulose dispersed in toluene.

The dispersion obtained was using a 0.152 mm thickness gauge applied to paper having a qelatin silver chloride emulsion layer. After drying, the obtained photographic

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BATH ORIGINAL

Material exposed through a line image and heated to 10 ° C for 3 seconds. This resulted in a developed and stabilized image.

Example 17

A solution was made from the following ingredients:

Succlnlmid 15.0 G Sodium isoascorbate 2.5 G 1-phenyl-3-pyrazolidone 1.5 G Phenyltrimethylphosphonium
bromide 7.0 G water 20.0 ml

The resulting solution was dissolved in 93 g of a 7 # solution of Xthyl cellulose dispersed in toluene.

The obtained dispersion was made using a 0.203 mm coating knife applied to a paper having a quelatine / silver chloride emulsion layer After drying, the photographic material obtained was exposed through a line image original and heated at 155 ° C. for 5 seconds. Here a developed and get stabilized image.

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Example 18

A solution was made from the following ingredients:

Succinimide. 15, floor Sodium isoascorbate 2.5 g

1-phenyl-3-i ** pyr.azolidone 1.5 g

Trimethylsulfonium bromide 5.0 g

Water 20.0 ml

The resulting solution was dissolved in 93 g of a 7Sfigen solution of Ethyl cellulose dispersed in toluene.

The resulting dispersion was coated onto paper having a 4 * gelatin-silver chloride emulsion layer using a 0.152 mm coating meter. After drying, the photographic material obtained was exposed through a line image original and ^{heated to IJ (0} ° C. for 5 seconds. A developed and stabilized image was obtained in this way.

Example 19 \ ' - ■ ~

A solution was prepared from the following ingredients;

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BAD ORfGINAt

SuecInimide 15.0 g

Sodium isoascorbate - 2.5 g of l-phenyl-3-pyrazolidone 1.5 g

Ethyldimethylsulfoxonium

bromide 8.3 g

Water 20.0 ml

The resulting solution was in 93 g of a Tilgen solution of Ethyl cellulose dispersed in toluene.

The dispersion obtained was applied to a paper having a gelatin-silver chloride emulsion layer using a 0.102 on coating knife.After drying, the photographic material obtained was exposed through a line copy negative and then ^{heated at 155 °} C. for 3 seconds.This resulted in a developed and stabilized image obtain·

Example 20

The following example describes the production of a dry developer tape

j I

A solution was made from the following ingredients:

ORIGINAL

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Suoolnlald 10.0 g Urea 10.0 g NttriuBltffcscorbate 2.5 g

1-phenyl-3-pyratolidone 1.5 g

Tttraäthylammonumbromid 10, Og

Waster. 20.0 ml

DIt received * Solder was in 45 g of a 15XIgen solution of Cellulose acetate butyrate dispersed in toluene.

The obtained dispersion was made using a 0.254 mm coating knife applied to a paper support widening a gelatin layer.

One sheet of a gelatin silver chloride layer having paper was exposed through a line copy negative and then with the described paper developer

The tape brought into contact with the resulting sandwich was heated paper side down on a 155 ° C mandrel for 5 seconds. After the two papers had separated, a developed and stabilized image had formed on the exposed paper.

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Example 21

In this example, a tropolone boron ion halide is used a non-aqueous system used as a complexing agent for silver halide *

The tropolone boronium bromide used was prepared as follows:

Under a nitrogen atmosphere, 5 g (0.02 moles) Borobromide Dissolved in 25 ml of chloroform. By dissolving 4.9 g (0.04 hole) Tropolone in 120 ml of chloroform under nitrogen A second solution was prepared. The two solutions were mixed together and heated to reflux temperature for 3 hours. During this time, a continuous on Nitrogen flow passed through the reactor quenching to remove the to remove hydrogen bromide formed during the reaction The reaction mixture was finally transferred to an evaporating dish transferred and left to stand overnight in a drying cabinet

The resulting reaction product, a yellow cake, turned off Recrystallized water, with 5.6 g of tropolone boronum bromide of the following formula:

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· An analysis of the compound obtained resulted in the following values: ''

Theoretically: Found:

C. 3 H 0 2 B. Br 5Q.3 3 , 0 19th 4 * 3.2 24.0 50.8 .2 19 3.5 23.2.

calculated from the difference

Tropolone boroniurobromide is soluble in water, formamide and melted succinimide. A 5X aqueous solution showed no tendency to silver chloride or silver bromide eu to solve. A 5 # solution in formamide (or melted Sucoinimide), on the other hand, dissolved silver chloride and silver bromide

very quickly.

Example 22

In this example, a tropolone siliconium chloride is used as Silver M-ogenide complexing agent used.

.0098 24/158 7

The tropolone siliconium chloride used was as follows manufactured

A solution of 4.6 g (0.028 mole) in 50 ml of chloroform was Siliciumtetraohlorid 4m below a solution of 10 g (0.08 Hole) tropolone sugegeben in 150 ml of chloroform. After the addition, the mixture was? Heated to reflux temperature for hours, a rapid stream of nitrogen being passed through the reaction mixture. After heating for 7 hours, no more hydrogen chloride escaped from the reaction vessel. A further, thick precipitate had deposited. This was filtered off and uakristallisiert on Waster, where-

I. -t

at 10.2 g of tropolone silicone chloride of the following formula

was received

An analysis

! he received connection

Cl '

resulted in the following values

BAD'ORIGINAL -

41

Theoretically C- 48.2 | H - 2.9 | Cl - 6.8 Found: C- * .8.9 | H- 3.4 $ Cl- 6.1

An IQ * aqueous solution of tropolone siliconium chloride ■ • igt · no · inclination, silver chloride or silver bromide eu to solve. A 10% solution in formamide (or melted Suoolnieid), on the other hand, dissolved silver chloride.

Β 1ιρ1 1 2}

The ··· example shows the suitability of a mixture of a quaternary halide and succinimide for stabilization • Ine · silver halide!) Ildeβ at room temperature. In order to lower the crystallization point of the mixture eu, a larger amount of water used.

A solution to the following combination can be found in Badfox «as well as by superficial application by means of a funnel or an orphan:

Succinimide 26.0 G Tetraethylan monlumbroBid 20.0 ε water '120.0 ml Dimethyl sulfoxide 15.0 ml

2% aqueous solution of a surfactant, consisting of isooctylphenylpolyethoxyethanol. 6.0 ml

00 98 24 / 1B87 - -

BAD ORJGJNAL

A photographic paper coated with a fine-grain silver chloride emulsion was exposed to light using a developer with the following composition :

Water, about 5O ⁰ C 500 ml p-methylaminophenol sulfate 3.0 g Sodium sulfite ^ dried 45th floor Hydroquinone 12.0 g Sodium carbonate, monohydrate 80, Ö ^r g Potassium bromide 2.0 g Topped up with water 1.0 liter

and diluted with water in a ratio of 1: 1 and then stabilized by letting it overflow twice over a roller immersed in the specified stabilizer solution. After drying with warm air for 20 to 30 seconds, the samples were stable to light. After three days of incubation at 25 ° C and 75 % relative humidity, no signs of image fading could be seen. Furthermore, no signs of stickiness could be found under such high humidity conditions.

009824/1587

Claims (1)

1. The use of onium halides, consisting of organic sulfonium, sulfonium, ammonium, phosphonium, boronium or siliconium halides and mixtures thereof in silicon halide emulsion layers or these adjacent layers in concentrations of at least 0.5 moles of onium halide / mole of silver halide or in fixing solutions at concentrations of 0.1 to 60 wt -.% / liter of solution as a silver halide complexing photographic for stabilizing silver halide images. 2. Use of onium halides according to claim 1, characterized in that they have the following general formulas: R, R- χ ^θ , Λ * t R ₁ , -R- and 009824/1587 BAD OR - U 2 - correspond, * where mean: A is a sulfur atom or a group of the formula SO; A ¹ a. Nitrogen, boron or phosphorus atom; A "is a silicon atom; X ^; a halogen ion and R ₂ , and Rg individually in each case hydrogen atoms or optionally substituted amino, alkyl or aryl radicals, '. Hydroxy radicals or aliphatic or aromatic radicals with at least one ether bond or an oxa group or two of the radicals R ₁ , Rp, R ,, R ^, Rc and Rg together with the radicals A, A ¹ or A "form a saturated or unsaturated heterocyclic ring. O CD OO N) 3. Use of onium halides according to claims 1 and 2, characterized in that it is used in the form of an at least weight percent solution. 4. Use of onium halides according to claims 1 to 3, characterized in that they are in the form of a solution in formamide, dimethylsulfoxide, dimethylformamide, succinifiiid, SuIfamid, urea, acetamide or water are used, ■ • ORIGINAL BATHROOM 5. Use of onlum halides according to Claims 1 to. ¹ J, characterized ₉ that they consist of tetraethyl- ■■ ammonium bromide, 2-hydroxyethyl-trlmethylammonium bromide, tetrapropylammonium iodide, tetraethylphosphonium bromide or trlmethy1salf onium bromide « 6. Use of onlum halides according to claims 1-5 » characterized in that a solution of tetraethylammonium bromide or tetraethylphosphonium bromide in succinic imide is used 7 «Use of onlum halides according to claims in 6, characterized in that they are used together with a polymeric binder « • -. ■ 6. Use of Oniuehalogeniden according to claims 1 to 7, characterized in that they are the silver halide mul aion of a photographic material incorporated. ■ ■■■ "- ■■■" ■■: - ■ / ' 9. Use of onium halides according to claims ijbis 7, characterized in that it is incorporated into a layer adjacent to the layer containing the silver halide. 10 · Use of onium halides according to claims 1 to 7 * characterized in that they are attached to a developer tape incorporated.